title: Electronic structure and photophysics of (C=C)tetra-p-tolylporphyrin2+.
abstract: The electronic structure and photophysical properties of (C=C)TTP(2+) (TTP = tetra-p-tolylporphyrin) were scrutinized by using quantum mechanical calculations and transient absorption spectroscopic measurements. When compared to a metalloporphyrin, the presence of the C=C unit in (C=C)TTP(2+) causes a splitting of the degenerate LUMO and a large decrease in the HOMO-LUMO gap, while the 2+ charge and tolyl groups lead to additional charge-transfer-like transitions in the visible absorption spectrum. The small HOMO-LUMO gap and ruffled structure lead to a very short excited-state lifetime of 10 ± 0.3 ps.
authors.affiliation: Department of Chemistry, Yonsei University, Shinchon-dong 134, Seodaemoon-gu, Seoul, 120-749, Republic of Korea. dongho@yonsei.ac.kr.
authors.forename: Young Mo
authors.initials: YM
authors.lastname: Sung
authors.forename: Monica
authors.initials: M
authors.lastname: Vasiliu
authors.forename: David A
authors.initials: DA
authors.lastname: Dixon
authors.forename: Marco
authors.initials: M
authors.lastname: Bonizzoni
authors.forename: Dongho
authors.initials: D
authors.lastname: Kim
authors.forename: Thomas P
authors.initials: TP
authors.lastname: Vaid